阅读说明：本技术 电催化析氢合金及其制备方法 (Electrocatalytic hydrogen evolution alloy and preparation method thereof ) 是由 杨超 付超鹏 柳昭慧 疏达 孙宝德 于 2021-09-18 设计创作，主要内容包括：一种电催化析氢合金及其制备方法,属于电化学催化技术领域。电催化析氢合金的组分包括Fe、Cr、Ni、V和Ti,电催化析氢合金包括体心立方结构的NiFeCrVTi固溶体相,且表面具有凹槽。该电催化析氢合金同时具有良好的电催化析氢效果以及在海水中的长循环稳定性。(An electro-catalytic hydrogen evolution alloy and a preparation method thereof, belonging to the technical field of electrochemical catalysis. The electrocatalytic hydrogen evolution alloy comprises Fe, Cr, Ni, V and Ti, and comprises a NiFeCrVTi solid solution phase with a body-centered cubic structure, and the surface of the electrocatalytic hydrogen evolution alloy is provided with grooves. The electrocatalytic hydrogen evolution alloy has good electrocatalytic hydrogen evolution effect and long circulation stability in seawater.)

1. The electrocatalytic hydrogen evolution alloy is characterized by comprising the components of Fe, Cr, Ni, V and Ti, and comprises a NiFeCrVTi solid solution phase with a body-centered cubic structure, and the surface of the electrocatalytic hydrogen evolution alloy is provided with grooves.

2. The electro-catalytic hydrogen evolution alloy of claim 1, wherein the grooves comprise a plurality of cavities, wherein some of the cavities are connected together to form corrugations, and wherein the area of the grooves is 50-90% of the surface area of the electro-catalytic hydrogen evolution alloy.

3. The electrocatalytic hydrogen evolution alloy of claim 2, wherein the diameter of the pits is 100nm to 5 μ ι η;

and/or the component of the electrocatalytic hydrogen evolution alloy is Ni_aFe_bCr_cV_dTi_eWherein a, b, c, d and e are respectively the mole percentage of each element, 0<a is less than or equal to 20, b is less than or equal to 20 and less than or equal to 40, c is less than or equal to 20 and less than or equal to 10, d is less than or equal to 35 and less than or equal to 5, e is less than or equal to 20, and a + b + c + d + e is 100.

4. A method for preparing an electrocatalytic hydrogen evolution alloy as set forth in any one of claims 1 to 3, comprising:

smelting Fe, Cr, Ni, V and Ti metal into an alloy ingot, preparing the alloy ingot into powder particles, and sintering the powder particles at 900-1100 ℃ and 30-50 MPa to obtain a primary product, wherein the primary product contains a NiFeCrVTi solid solution phase with a body-centered cubic structure and Ni with a face-centered cubic structure₃Ti；

Subjecting the Ni on the surface of the primary product₃Ti is etched to form the electro-catalytic hydrogen evolution alloy with the groove on the surface.

5. The preparation method of the electrocatalytic hydrogen evolution alloy as set forth in claim 4, wherein the etching mode is laser etching, and the laser power of the laser etching is 10-40W.

6. The preparation method of the electrocatalytic hydrogen evolution alloy as set forth in claim 5, wherein the laser etching time is 2-5 min.

7. The method for producing an electrocatalytic hydrogen evolution alloy as set forth in any one of claims 4 to 6, wherein the powder particles having a particle size of 150 to 300 μm are sintered.

8. The method for preparing an electrocatalytic hydrogen evolution alloy as set forth in any one of claims 4 to 6, wherein the step of melting the Fe, Cr, Ni, V and Ti metals into an alloy ingot comprises:

and melting and mixing the Fe, the Cr, the Ni, the V and the Ti, solidifying to obtain an ingot, turning the ingot for multiple times, and smelting to obtain the alloy ingot.

9. The method for preparing the electrocatalytic hydrogen evolution alloy as set forth in claim 8, wherein the angle of each turn of the ingot is 30 to 50 °.

10. The method for preparing an electrocatalytic hydrogen evolution alloy as set forth in claim 8, wherein the V, Ni, Fe, Ti and Cr metals are layered in sequence from bottom to top and then smelted.

Technical Field

The application relates to the technical field of electrochemical catalysis, in particular to an electrocatalytic hydrogen evolution alloy and a preparation method thereof.

Background

The hydrogen energy has the characteristics of high combustion heat value, pollution-free water as a product, rich resources and the like, is one of the cleanest energy sources in the world, is also an important chemical raw material, and is widely regarded by countries in the world. In the conventional hydrogen production method, the hydrogen production by electrolyzing water is an important means for realizing industrialized and cheap hydrogen production. Electrochemical hydrolysis involves two half-reactions, Hydrogen Evolution (HER) and Oxygen Evolution (OER), the efficiency of which is the determining factor in the determination of electrolyzed water.

The high-entropy alloy has the structural characteristics of disordered occupancy and ordered crystal lattices, and the wide component modulation range and the inherent complex surface provide possibility for obtaining an adsorption energy curve which is nearly continuously distributed. The configuration entropy of the system can be increased by uniformly mixing multiple components, and a single-phase solid solution structure with stable entropy driving, thermodynamics and kinetics can be further constructed, so that the single-phase solid solution structure can be kept relatively stable in severe service environments (high temperature, corrosion and high electrochemical potential). The high-entropy alloy is taken as a research hotspot of material science in recent years, and attracts wide attention of global researchers, and the preparation method of the high-entropy alloy nano structure is a base stone of the high-entropy alloy in the field of catalysis, and is already applied to design of an electrocatalyst.

Electrocatalysis is mostly based on alkaline aqueous solution, and the search for an electrocatalysis electrode material which has good hydrogen evolution effect and can realize long-term stable circulation in seawater is particularly important for the development of seawater electrolysis.

Disclosure of Invention

The application provides an electrocatalytic hydrogen evolution alloy and a preparation method thereof, and the electrocatalytic hydrogen evolution alloy has good electrocatalytic hydrogen evolution effect and long circulation stability in seawater.

The embodiment of the application is realized as follows:

in a first aspect, embodiments of the present application provide an electrocatalytic hydrogen evolution alloy, the components of which include Fe, Cr, Ni, V, and Ti, and the electrocatalytic hydrogen evolution alloy includes a NiFeCrVTi solid solution phase with a body-centered cubic structure, and the surface of which has grooves.

In a second aspect, embodiments of the present application provide a method for preparing an electrocatalytic hydrogen evolution alloy of the embodiments of the first aspect, including:

smelting Fe, Cr, Ni, V and Ti metal into an alloy ingot, preparing the alloy ingot into powder particles, and sintering the powder particles at the temperature of 900-1100 ℃ and the pressure of 30-50 MPaObtaining a primary product containing NiFeCrVTi solid solution phase with body-centered cubic structure and Ni with face-centered cubic structure₃Ti；

Ni on the surface of the primary product₃Ti is etched to form the electro-catalytic hydrogen evolution alloy with the groove on the surface.

The electrocatalytic hydrogen evolution alloy and the preparation method thereof provided by the embodiment of the application have the following beneficial effects:

the surface of the electrocatalytic hydrogen evolution alloy provided by the embodiment of the application is provided with the grooves, so that the specific surface area of the electrocatalytic hydrogen evolution alloy can be increased, and the electrocatalytic hydrogen evolution alloy contains a NiFeCrVTi solid solution phase with a body-centered cubic structure, so that the electrocatalytic efficiency of the electrocatalytic hydrogen evolution alloy can be improved, and the electrocatalytic hydrogen evolution alloy has good circulation stability in seawater.

In the preparation method of the embodiment of the application, the atomic radii of Fe, Cr, Ni, V and Ti elements are close and easy to form a solid solution phase, the alloy ingot obtained by smelting is prepared into powder particles, and the powder particles are sintered at the temperature of 900-1100 ℃ and the pressure of 30-50 MPa to obtain the NiFeCrVTi solid solution phase containing a body-centered cubic structure and the Ni containing a face-centered cubic structure₃Ti，Ni₃Ti and NiFeCrVTi solid solution phase interface with body-centered cubic structure are not coherent, Ni₃Ti can be easily etched away, so that the electrocatalytic hydrogen evolution alloy with the grooves on the surface is formed.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.

FIG. 1 is an XRD pattern of an electrocatalytic hydrogen evolution alloy of example 1 of the present application;

FIG. 2 is an SEM image of an electro-catalytic hydrogen evolution alloy (after etching) of example 1 of the present application;

FIG. 3 is an SEM image of an electro-catalytic hydrogen evolution alloy (after etching) of example 5 of the present application;

FIG. 4 is an SEM image of an electrocatalytic hydrogen evolution alloy of comparative example 1 of the present application (without etching);

FIG. 5 is a hydrogen evolution overpotential test chart of an electrocatalytic hydrogen evolution alloy of example 1 and comparative example 1 of the present application and Pt;

FIG. 6 is a Tafel plot of electrocatalytic hydrogen evolution alloys of example 1 of the present application, comparative example 1 and Pt;

FIG. 7 is a graph showing the cycle performance of the electrocatalytic hydrogen evolution alloy of example 1 of the present application.

Detailed Description

Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The following description will be made specifically for the electrocatalytic hydrogen evolution alloy and the preparation method thereof in the embodiments of the present application:

in a first aspect, embodiments of the present application provide an electrocatalytic hydrogen evolution alloy, the components of which include Fe, Cr, Ni, V, and Ti, and the electrocatalytic hydrogen evolution alloy includes a NiFeCrVTi solid solution phase with a body-centered cubic structure, and the surface of which has grooves.

The surface of the electrocatalytic hydrogen evolution alloy provided by the embodiment of the application is provided with the grooves, so that the specific surface area of the electrocatalytic hydrogen evolution alloy can be increased, and the electrocatalytic hydrogen evolution alloy contains a NiFeCrVTi solid solution phase with a body-centered cubic structure, so that the electrocatalytic efficiency of the electrocatalytic hydrogen evolution alloy can be improved, and the electrocatalytic hydrogen evolution alloy has good circulation stability in seawater. The research of the inventor of the application shows that if the surface of the electrocatalytic hydrogen evolution alloy is smooth, the photocatalytic hydrogen evolution effect is greatly reduced.

The groove comprises a plurality of concave holes, part of the concave holes in the plurality of concave holes are connected together to form a gully, and the area of the groove accounts for 50-90% of the surface area of the electro-catalytic hydrogen evolution alloy.

Optionally, the area of the grooves comprises any one of, or a range between any two of, 50%, 60%, 70%, 80%, and 90% of the surface area of the electrocatalytic hydrogen evolution alloy.

Illustratively, the diameter of the pits is 100nm to 5 μm, for example, in the range of any one or between any two of 100nm, 300nm, 500nm, 800nm, 1 μm, 2 μm, 3 μm, 4 μm, and 5 μm.

In some embodiments, the partially connected cavities have protrusions between them, which have been found by the research of the inventors of the present application to be advantageous for electrocatalytic hydrogen evolution.

In some embodiments, the electrocatalytic hydrogen evolution alloy also contains Ni inside₃Ti，Ni₃The presence of Ti can improve the strength of the electrocatalytic hydrogen evolution alloy.

In some embodiments, the component of the electrocatalytic hydrogen evolution alloy is Ni_aFe_bCr_cV_dTi_eWherein a, b, c, d and e are respectively the mole percentage of each element, 0<a is less than or equal to 20, b is less than or equal to 20 and less than or equal to 40, c is less than or equal to 20 and less than or equal to 10, d is less than or equal to 35 and less than or equal to 5, e is less than or equal to 20, and a + b + c + d + e is 100.

Illustratively, a is 0.5, 1, 2, 3, 5, 7, 8, 10, 12, 14, 16, 18, or 20.

Illustratively, b is 20, 22, 25, 28, 30, 32, 35, 38, or 40.

Illustratively, c is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

Illustratively, d is 5, 10, 15, 20, 25, 30, or 35.

Illustratively, e is 5, 8, 10, 12, 15, 18, or 20.

In a second aspect, embodiments of the present application provide a method for preparing an electrocatalytic hydrogen evolution alloy of the embodiments of the first aspect, including:

(1) smelting Fe, Cr, Ni, V and Ti metal into an alloy ingot, preparing the alloy ingot into powder particles, sintering at 900-1100 ℃ and 30-50 MPa to obtain a primary product, wherein the primary product contains NiFeCrVTi solid with a body-centered cubic structureSolution phase and face centered cubic structure of Ni₃Ti。

In the preparation method, the atomic radii of Fe, Cr, Ni, V and Ti elements are close, a solid solution phase is easy to form, powder particles are sintered at the temperature of 900-1100 ℃ and the pressure of 30-50 MPa, and the NiFeCrVTi solid solution phase containing a body-centered cubic structure and the Ni containing a face-centered cubic structure can be obtained₃Ti。

In some embodiments, powder particles having a particle size of 150 to 300 μm are sintered.

Illustratively, the powder particles have a particle size in any one or a range between any two of 150 μm, 180 μm, 200 μm, 220 μm, 250 μm, 280 μm, and 300 μm. Wherein, the alloy ingot can be made into powder particles by adopting an atomization powder-making mode.

In addition, optionally, the Fe, Cr, Ni, V, and Ti metals are smelted after descaling. Optionally, the purity of the Fe, Cr, Ni, V and Ti metal raw materials is more than 99.95%.

In some embodiments, the step of melting Fe, Cr, Ni, V, and Ti metals into an alloy ingot comprises:

and melting Fe, Cr, Ni, V and Ti, solidifying to obtain an ingot, turning the ingot for multiple times, and smelting to obtain an alloy ingot.

The ingot is turned over for multiple times and smelted, so that the distribution uniformity of the components can be improved. Herein, the plural times in the embodiment of the present application means two times or more.

Optionally, the angle of each turn of the ingot is 30-50 °, for example 30 °, 35 °, 40 °, 45 ° or 50 °.

Illustratively, V, Ni, Fe, Ti and Cr metals are sequentially layered from bottom to top and then smelted, wherein the layer with higher melting point among the elements is layered on the upper layer, and the layer with lower melting point is layered on the lower layer, so that the distribution uniformity of the components can be improved.

Optionally, the embodiment of the application can adopt a vacuum arc heating mode to heat and melt the metal element. In other embodiments, other heating methods, such as infrared heating, etc., may also be used, and the heating method is not limited in the examples of the present application.

In some embodiments, the sintering temperature is 900 ℃, 1000 ℃, or 1100 ℃.

Optionally, the sintering holding time is 5-15 min, for example, any one of 5min, 8min, 10min, 12min and 15min or a range between any two.

In some embodiments, the pressure of sintering is 30MPa, 35MPa, 40MPa, 45MPa, or 50 MPa.

(2) Ni on the surface of the primary product₃Ti is etched to form the electro-catalytic hydrogen evolution alloy with the groove on the surface.

Face centered cubic structure Ni₃Ti and NiFeCrVTi solid solution phase interface with body-centered cubic structure are not coherent, Ni₃Ti can be easily etched away, so that the electrocatalytic hydrogen evolution alloy with the grooves on the surface is formed. The primary product may contain Ni₃Ti, Ni inside the primary product₃Ti can not be etched away, and Ni can be contained in the electrocatalytic hydrogen evolution alloy₃Ti, when the inside of the electrocatalytic hydrogen evolution alloy contains Ni₃Ti can improve the strength of the electrocatalytic hydrogen evolution alloy.

In some embodiments, the etching mode is laser etching, and the laser power of the laser etching is 10-40W.

The inventors of the present application found in their research that Ni has a face-centered cubic structure₃Ti and NiFeCrVTi solid solution phase interfaces with body-centered cubic structures are not coherent, and Ni can be effectively etched by adopting proper laser power₃The Ti is etched away. Moreover, the laser etching method is adopted to electrically catalyze Ni on the surface of the hydrogen evolution alloy₃When Ti is etched, if the laser power is too small, Ni₃Ti is not easily etched away. In the embodiment of the application, when the primary product is etched by adopting the laser power of 10-40W, Ni on the surface of the primary product can be etched₃Ti is etched away, and the NiFeCrVTi solid solution phase matrix is slightly damaged.

Illustratively, the laser power of the laser etching is in a range between any one or any two of 10W, 15W, 20W, 25W, 30W, and 40W.

In some embodiments, the laser etching time is 2-5 min, such as 2min, 3min, 4min, or 5 min.

In other embodiments, the Ni on the surface of the primary product may be etched by other means such as plasma etching₃And (5) Ti etching.

The electrocatalytic hydrogen evolution alloy and the preparation method thereof are further described in detail with reference to the following examples.

Example 1

The embodiment provides an electrocatalytic hydrogen evolution alloy, and the preparation method comprises the following steps:

s1: removing surface oxide skin of Ni, Fe, Cr, V and Ti metals, weighing according to the proportion of alloy components, adding the weighed Ni, Fe, Cr, V and Ti metals into a vacuum arc furnace, sequentially layering the V, Ni, Fe, Ti and Cr from the bottommost layer, and smelting until all the metals are completely molten and uniformly fused.

S2: and (3) turning the molten and solidified cast ingot by 40 degrees by using a manipulator, smelting, turning by 40 degrees after smelting, and smelting, wherein the process is circulated for 4 times to obtain the alloy ingot.

S3: atomizing an alloy ingot to prepare powder, obtaining powder particles with the particle size of 150-200 mu m, and sintering the powder particles at the temperature of 1000 ℃ and under the pressure of 40MPa for 10min to obtain a NiFeCrVTi solid solution phase containing a body-centered cubic structure and Ni containing a face-centered cubic structure₃A Ti primary product, and laser etching the Ni on the surface of the primary product₃Ti is etched to form the electro-catalytic hydrogen evolution alloy with the groove on the surface. Wherein, the laser power is 20W, and the etching time is 4 min. The component of the electrocatalytic hydrogen evolution alloy is Ni_0.5FeCr_0.4V_1.1Ti_0.2。

Example 2

The embodiment provides an electrocatalytic hydrogen evolution alloy, and the preparation method comprises the following steps:

s1: removing surface oxide skin of Ni, Fe, Cr, V and Ti metals, weighing according to the proportion of alloy components, adding the weighed Ni, Fe, Cr, V and Ti metals into a vacuum arc furnace, sequentially layering the V, Ni, Fe, Ti and Cr from the bottommost layer, and smelting until all the metals are completely molten and uniformly fused.

S2: and (3) turning the melted and solidified cast ingot by 50 degrees by using a manipulator, smelting, then turning by 50 degrees, smelting, and circulating for 4 times to obtain the alloy ingot.

S3: atomizing an alloy ingot to prepare powder, obtaining powder particles with the particle size of 100-150 mu m, and sintering the powder particles at 1100 ℃ and under the pressure of 30MPa for 15min to obtain a NiFeCrVTi solid solution phase containing a body-centered cubic structure and Ni containing a face-centered cubic structure₃A Ti primary product, and laser etching the Ni on the surface of the primary product₃Ti is etched to form the electro-catalytic hydrogen evolution alloy with the groove on the surface. Wherein the laser power is 10W, and the etching time is 5 min. The component of the electrocatalytic hydrogen evolution alloy is Ni_0.5FeCr_0.4V_0.3Ti_0.2。

Example 3

The embodiment provides an electrocatalytic hydrogen evolution alloy, and the preparation method comprises the following steps:

s1: removing surface oxide skin of Ni, Fe, Cr, V and Ti metals, weighing according to the proportion of alloy components, sequentially layering the weighed V, Ni, Fe, Ti and Cr from the bottommost layer, and smelting until all the metals are completely molten and uniformly fused.

S2: and (3) turning the melted and solidified cast ingot by 50 degrees by using a manipulator, smelting, then turning by 50 degrees, smelting, and circulating for 4 times to obtain the alloy ingot.

S3: sintering the alloy ingot at 900 ℃ and 50MPa for 10min to obtain NiFeCrVTi solid solution phase with body-centered cubic structure and Ni with face-centered cubic structure₃A Ti primary product, and laser etching the Ni on the surface of the primary product₃Ti is etched to form the electro-catalytic hydrogen evolution alloy with the groove on the surface. Wherein the laser power is 30W, and the etching time is 2 min. The component of the electrocatalytic hydrogen evolution alloy is NiFeCrVTi.

Example 4

The embodiment provides an electrocatalytic hydrogen evolution alloy, and the preparation method comprises the following steps:

s1: removing surface oxide skin of Ni, Fe, Cr, V and Ti metals, weighing according to the proportion of alloy components, adding the weighed Ni, Fe, Cr, V and Ti metals into a vacuum arc furnace, heating and melting, and solidifying to obtain an alloy ingot.

S2: sintering the alloy ingot at 950 ℃ and 45MPa for 12min to obtain NiFeCrVTi solid solution phase with body-centered cubic structure and Ni with face-centered cubic structure₃A Ti primary product, and laser etching the Ni on the surface of the primary product₃Ti is etched to form the electro-catalytic hydrogen evolution alloy with the groove on the surface. Wherein, the laser power is 25W, and the etching time is 3 min. The component of the electrocatalytic hydrogen evolution alloy is Ni_0.2Fe_0.8Cr_0.4V_0.3Ti_0.3。

Example 5

This example provides an electrocatalytic hydrogen evolution alloy, which is prepared by a method different from that of example 1 only in the laser power, which is 5W.

Comparative example 1

The comparative example provides a preparation method of an electrocatalytic hydrogen evolution alloy, and compared with the example 1, the difference is that the comparative example 1 omits the Ni on the surface of the primary product by adopting a laser etching mode in the example 1₃And (5) Ti etching.

Test example 1

The X-ray diffraction test was carried out on the electrocatalytic hydrogen evolution alloy prepared in example 1, and the results obtained are shown in fig. 1.

From the results of fig. 1, it can be seen that the electrocatalytic hydrogen evolution alloy contains a NiFeCrVTi solid solution phase (bcc phase) of a body-centered cubic structure.

Test example 2

The electrocatalytic hydrogen evolution alloys prepared in example 1, example 5 and comparative example 1 were observed under an electron scanning microscope, and SEM images obtained are shown in fig. 2 and fig. 3.

As can be seen from fig. 2, the surface of the electrocatalytic hydrogen evolution alloy prepared in example 1 of the present application has grooves, wherein the arrows in fig. 2 indicate the grooves, and the grooves are distributed over the entire surface of the electrocatalytic hydrogen evolution alloy.

As can be seen from FIG. 3, the surface of the electrocatalytic hydrogen evolution alloy prepared in the example 5 also has some Ni₃Ti is not etched away (Ni at the position indicated by the arrow in FIG. 3)₃Ti) which indicates that Ni on the surface of the alloy which is subjected to electrocatalytic hydrogen evolution cannot be effectively removed when the laser power is too small₃The Ti is etched away.

In addition, as can be seen from FIG. 4, the surface of the electrocatalytic hydrogen evolution alloy prepared in comparative example 1 has Ni₃Ti, not laser etched, Ni₃Ti is also incorporated in a body-centered cubic NiFeCrVTi solid solution phase. The laser etching method of the embodiment 1 of the application can effectively remove Ni on the surface of the electro-catalytic hydrogen evolution alloy₃The Ti is etched away.

Test example 3

The electrocatalytic hydrogen evolution alloy prepared in example 1 and comparative example 1 and platinum (Pt) were used as working electrode materials, and the electrolyte was an aqueous solution containing NaCl, and the tests of the electrocatalytic hydrogen evolution performance were performed, wherein the mass concentration of NaCl was 3.5%, and the tests included hydrogen evolution overpotential test: a three-electrode cell tank is adopted, a working electrode is a corresponding electro-catalytic hydrogen evolution alloy, a counter electrode is a carbon rod, a reference electrode is a saturated calomel electrode, and the electro-catalytic hydrogen evolution performance is measured on a constant potential rectifier by adopting a linear plan. Tafel curves are according to the formula: η ═ b log j + a (j is the current density and b is the Tafel slope) and the obtained graphs are shown in fig. 5 and 6, respectively. Wherein the current density adopted by hydrogen evolution overpotential test is 10mA/cm²。

As can be seen from fig. 5, the hydrogen evolution overpotential (LSV) of the electrocatalytic hydrogen evolution alloy of example 1 was 73.9mV, the hydrogen evolution overpotential ratio of platinum was 27.9mV, and the hydrogen evolution overpotential ratio of the electrocatalytic hydrogen evolution alloy of example 1 was less different from that of platinum. The hydrogen evolution overpotential (LSV) of the electrocatalytic hydrogen evolution alloy of comparative example 1 was 488.7mV, which was much worse than that of platinum. Wherein, the smaller the hydrogen evolution overpotential value is, the easier the material is to evolve hydrogen, which indicates that the hydrogen evolution capacity of the electrocatalytic hydrogen evolution alloy of the embodiment 1 is far greater than that of the electrocatalytic hydrogen evolution alloy of the comparative example 1.

As can be seen from FIG. 6, the Tafel value of the electrocatalytic hydrogen evolution alloy of example 1 was 56.5mV dec^-1The Tafel value of platinum is 67.8mV dec^-1The Tafel value of the electrocatalytic hydrogen evolution alloy of comparative example 1 was 121.5mV dec^-1The tafel value is used for representing the reaction kinetics of the material, and the smaller the tafel value is, the more favorable the reaction is, and the above experimental result shows that the electrocatalytic hydrogen evolution alloy of the embodiment 1 of the present application is favorable for the hydrogen evolution reaction.

Test example 4

The electrocatalytic hydrogen evolution alloy prepared in example 1 was used as an electrode material, seawater was electrolyzed, and the stability of the electrode material after 30 hours of circulation was tested, and the results are shown in fig. 7. Wherein, the mass concentration of NaCl in the seawater is 3.5%.

As can be seen from fig. 7, the electrocatalytic hydrogen evolution alloy of the embodiment 1 of the present application has good cycle stability when electrocatalytic in seawater.

The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.